Oxygen-treated hydrocarbon resins



Patented July 20, 1948 OXYGEN-TREATED HYDROCARBQN RESINS AND COMPOSITIONS CONTAINING THE SAME Frank J. Soday, Baton Rouge, La., assignor to The United Gas Improvement Company, a cor- V poration of Pennsylvania No Drawing. Application June 20, 1944, Serial No. 541,263

6 Claims. (Cl. 260-23) drying properties. I A feature of the invention is the provision of drying oil coating compositions comprising a resin of the type described dissolved in a bodied drying oil. Pigments, fillers, coloring agents, driers, anti-skinning agents, plasticizers, softeners, solvents, particularly hydrocarbon solvents, and/or other additives, also may be incorpoarted in such coating compositions, if desired.

Coating compositions comprising a resin dissolved in a mixture of bodied drying oil and 9. volatile hydrocarbon solvent have long been employed in the industry for coating a variety of surfaces, such as those of wood and steel. Among these coating compositions are those prepared from dark-colored resins and employed for painting surfaces where a colorless coating is not required. Examples of these coating compositions are varnishes, paints, and enamels used for coating structural steel surfaces in general, agricultural implements, the under surface of car bodies, railroad rolling and stationary stock, and the like.

In general, it may be said that the most important requirements for such coating compositions are (1) the ability to adhere to metallic or other surfaces for prolonged periods of time without checking, scaling, cracking, or other signs of disintegration, (2) the ability to protect the.

. coated surface from attack by moisture or other destructive agents, (3) resistance to deterioration by actinic rays, (4) resistance to abrasion or other mechanical attack, (5) resistance to attack by, mild acid or alkaline agents or solutions, and the absence of any reactive or corrosive agents in the coating compositions.

While coating compositions of the type described are commonly prepared from certain natural and artificial resins, such as rosin, gilsonite, petroleum pitch, still residues obtained as a by-product of the distillation of hydrocarbon stocks, resins obtained as a icy-product of the solvent extraction of lubricating stocks. other hydrocarbon resins, and the like, such coating compositions have not been entirely satisfactory from all standpoints. Thus, for example, coating films prepared from such coating compositions usually fail within a short period of time upon exposure to the atmosphere.

In my copending application, Serial No. 423,304, filed December 17, 1941, which has matured intoPatent 2,395,076, dated February 19, 1946, I have disclosed the use of the resin obtained by the thermal and/or catalytic polymerization of the unsaturated monomeric material boiling within the range of from 210 to 350 (3., and separated in monomeric form from higher boiling pitch constituents of the tar formed during the production of gas by processes involving the pyrolytic decomposition of petroleum oil, with or without the aid of catalysts, in the preparation of coating compositions of the drying oil type. Such coating compositions possess outstanding properties, particularly from the standpoint of coating metallic surfaces.

I have now discovered that the drying time of such coating compositions'may be largely improved by the removal of certain natural inhibitors present in such resins prior to use,. and that this may be accomplished by contacting the said resin, 9. solution of the resin in a suitable solvent, or the monomeric material prior to polymerization, with oxygen or oxygen-yielding agents. I

.I have further discovered that such resins are soluble in, or compatible with, the less expensive drying oils, such as, for example, linseed, flsh, periila, soya, and similar oils, or mixtures thereof, and the less expensive hydrocarbon solvents, such as, for example, mineral spirits and V. M. and P. naphtha, and/or mixtures thereof with aromatic hydrocarbons. Thus, they are ideally suited for the prepartion of fairly inexpensive compositions designed to coat a wide variety of surfaces, such as wood, metal, cement, concrete, brick, ceramic, or other surfaces.

The hydrocarbon constituents of petroleum tar of the type described have usually been considered to comprise residual tar, dead oil, and light oil. The residual tar comprises the heavy black pitch constituents of the tar, together with any oil'unseparated therefrom. The dead oil comprises oil separated from the residual tar and boiling higher than, say, 200-210 C. The light oil comprises oil separated from residual tar and boiling lower than, say, 200-210 C.

It has been discovered that very considerable quantities of such resin-forming unsaturated monomeric material above referred to, including large quantities of readily heat polymerizable material, may be contained in the tar produced in the vapor phase pyrolysis of crude petroleum oil or a fraction or fractions thereof, such as, for example, gas oil or residuum oil. This is particularl-y so in the case of petroleum oil gas tar produced when the pyrolysis is conducted at relatively high temperatures, such, for example, as in the manufacture of oil gas or carburetted water gas at average set temperatures above 1300 F. and also particul'arly so when the oil pyrolyzed is naphthenic, such as a crude oil classifiable in classes to 7, inclusive, according to the method of classification described in Bureau of Mines Report of Investigations 3279, or a fraction or fractions of such an oil.

The possibility of recovering large quantities of resin forming monomeric unsaturated material boiling in .the dead oil range was long unrealized. This was because the usual distillation procedures for the purpose of petroleum tar dehydration and/or tar fractionation were such as to polymerize'the readily heat polymerizabie monomers boiling in the dead oil range into heavy polymers, which were inextricably mixed with the heavy black residual pitch constituents and lost therein. In copending application Serial Number 370,608, filed December 18, 1940. by Edwin L. Hall and Howard B. Batchelder, which has matured into Patent 2,387,259, dated October 23, 1945, such heat poiymerlzable monomeric hydrocarbons boiling in the range of from 210 to 350 C. and separated from the heavy black pitch constituents of the petroleum tar are described and claimed, together with heat polymers produced therefrom.

In I copending application Serial Number 386,232, filed April 1, 1941, by Waldo C. Ault. which has matured into Patent 2,387,237, dated October 23, 1945, there is described and claimed the production of catalytic resins from the heat poiymerizable and/or catalytieally poiymerizable' monomeric hydrocarbons boiling within the range of from 210 C. to 350 C. and separated in monomerie form from the heavy black pitch constitucuts of the petroleum tar.

In the manufacture of oilgas and carburetted water gas, the tar produced is usually in the form of' an emulsion due to the condensation of hydrocarbon constituents from the gas in the presence of water simultaneously condensed from theses or otherwise present.

In copending application 342,735, filed June 27, 1940, by Edwin L. Hall and Howard R. Batchelder, which has matured into Patent 2,366,899, dated January 9, 1945, there is described a method of dehydrating such petroleum tar emulsions and of fractionating the hydrocarbon constituents thereof by rapid distillation with the separation from the heavy pitch constituents of residual tar of such heat polymerizable unsaturated monomerichydrocarbons boiling in the dead oil range.

In copending application 353,034, filed August 17, 1940, by Howard R. Batchelder, which ha matured into Patent 2,383,362, dated August 21, 1945, there is described the dehydration of such petroleum tar emulsions and the fractionation of the hydrocarbon constituents thereof with the recovery of monomeric unsaturated heart polymerizable dead oil constituents separate from the heavy black pitch constituents of residual tar, by the I solvent extraction of the emulsion with a hydrocarbon solvent such as liquefied propane or butane.

Other processes, for example fractional condensation, might be employed to recover these relatively high boiling unsaturated hydrocarbons in monomeric form and separate from the heavy black pitch constituents of the tar. Also, processes for oil pyrolysis which avoid the formation of emulsions, may be employed for the production of the monomeric material. Furthermore, while it may be preferred to employ for pyrolysis petroleum oils or cuts therefrom, which are classifiable in classes 5 to 7 inclusive according to Bureau of Mines Report of Investigations 3279 as indicated above, and particularly those in class 7, other oils may be employed.

Whatever process of oil pyrolysis is employed in the production of this monomeric material, and whatever process is employed for arating the resultant tar, a very important factor is the exercise of care in the treatment of the tar in order to avoid excessive polymerization of these readily heat poiymerizable dead oil constituents and their loss as polymers mixed with the heavy black pitch constituents of the residual tar.

As a result of separation of the light oil and dead oil components of the products of such petroleum oil pyrolysis from the residual tar, without polymerization or with materially reduced polymerization, a substantially pitch-free hydrocarbon material may be separated having a portion boiling within the range from 210 C. to 350 C. which may contain from 5% to 30%, and higher, of monomeric unsaturated hydrocarbons readily polymerizable by heat.

The particular concentration of this heat polymerizable monomeric material obtained in a given case will depend upon the amount of polymerize:- tion produced in separating it fromthe residual tar, as well as upon such factors as the conditions of pyrolysis and the character of the petroleum oil pyrolyzed.

As previously stated, the above mentioned heat polymerizable monomeric material may be readily polymerized by heat to form valuable resins.

Polymerization may be effected by heating the total material separated from the residual tar sufficiently to polymerize the readily heat polymerizable monomers boiling within the range of from 210 to 350 C., but insufficiently to appreciably polymerize the heat polymerizable. material contained in lower boiling ranges, such, for

instance, as methyl styrenes and styrene. This may be accomplished, for example, by heating with stirring for 4 hours at 200 C., followed by distillation under vacuum to isolate the resin.

It may be preferable, however, to first effect a separation by fractional distillation between light oil boilingbelow, say, 210 C. and dead oil boilinB above, say, 210 C.

The heat polymerizable monomeric material boiling within the range of 210 to 350 C. is so readily polymerizable by heat, that, in the fractional distillation of the light oil from the dead oil, a portion of the monomeric material is usually unavoidably polymerized and remains as p mer dissolved in the other constituents of the dead oil after the light oil is taken off overhead.

The polymerization of the heat polymerizable unsaturated monomeric material in the separated dead oil may be effected by heating the dead oil with stirring, for example, for four hours at 200 The resin thus produced, together with any resin produced during the separation of the light oil from the dead oil, may then be isolated by distillation under vacuum.

In the separation of lower boiling hydrocarbon material from the pitch constituents of residual tar by various methods, the oil separated may contain components boiling above 350 C. and theremay be present heat polymerizable monomeric material boiling outside the range of from 210 C. and 350 C. together with the monomeric material boiling within that range. On polymerization therefore the resin may include polymers derived from monomers boiling outside said range along with polymers derived from mono- 'mers boiling within said range.

As herein before stated, after polymerization the resin may be isolated by distillation in vacuum, which may be assisted by steam. The yield, melting point, and other characteristics of the resin will depend upon the extent to which the isolation has been carried, "or, in other words, upon the proportion of associated oils left in the resin.

Exhaustive steam distillations oi the resins obtained from the unsaturated monomeric material isolated from tar by the distillation or solvent extraction methods described herein have produced resins having melting points as high as from 185 C. to 200 C. and higher, cube in mercury, as determined by the method and apparatus described in A. S. T. M. Procedure D61-24, with the following modifications. a

1. Mercury is employed in depthof 2 inches instead of water.

2. The cube of resin is rigidly supported by clamping the hook upon which the resin is attached so that the top of the cube is 1 inch below the surface of the mercury.

3. A 1 inch immersion thermometer is employed and is immersed to that depth.

4. The exact temperature at which the resin becomes visible at the surface of the mercury is 7 recorded asthe softening point of the resin.

5. The melting point of the resin is calculated from the softening point by the following formula.

Melting point C.=

\ softening point C. 1.25+2 C.

The melting point of the resins described in this specification is intended to mean melting point as determined by the above recited method, unless otherwise specified.

Lower melting point resins may be readily ob-: tained in greater yields by less exhaustive removal of the associated oils, thus resins ranging from very soft to hard resins having high melting points may be obtained as desired. 1

It has been usually found that each 6% of associated oils left in the resin lowers the melting point about 10 C.

Heat resins having melting points of 120 C. have been readily produced in yields corresponding to to of the dead oil in the case of the tar distillate produced in accordance with the process described in copending application Serial No. 342,735, and resins of the same melting point have been obtained in yields as high as 60% of the dead oil in the case of dead oil separated from extract produced in the process described in application Serial No. 353,034.

The heat polymerizable unsaturated monomeric material is preferably in sufficient concentration in that portion of the hydrocarbon material separated from the residual tar which boils within the range of from 210 to 350 C. to produce on polymerization by heat a 120 C. meltingpoint resin in quantity equal to at least 10 percent of the hydrocarbon material boiling within the range from 210 C. to 350 C., and preferably at separated from residual tar by the distillation process described in said copending application, Serial No. 342,735, have shown a tendency to be lighter in color than those produced from dead oil obtained from the solvent extraction of tar with propane and butane as described in said copending application, Serial No. 353,034. Also, heat polymer resins produced from the lower boiling portions of the dead oil have shown a tendency to be lighter in color than heat polymer resins produced from the higher boiling portions, especially such a portion as that boiling in a dead oil out taken from 180 C. to 210 C. under a vacuum equivalent to 20 mm. of mercury, absolute.

The following example will serve to illustrate the preparation of resins from such unsaturated fractions by thermal polymerization methods.

Example 1 Approximately 1000 grams of dead oil derived from the rapid distillation of oil gas tar in accordance with the process described in said copending application, Serial No. 342,735, and subtransferred for distillation to a tared 2-liter flask equipped with a ground glass neck.

The oil was accurately weighed at this point. The flask was provided with means for measuring vapor temperatures and was connected with condensing apparatus and with means for'providing a vacuum including a pressure control device. Bumping during distillation was avoided by folding several folds of iron wire to such length that one end reached slightly into the neck of the flask while the other end rested on the bottom of the flask. I

The pressure was reduced to mm. Hg, absolute, and heat applied by means of a Bunsen burner. The distillation was continued at a pressure of 100 mm. Hg absolute, until the vapor temperature reached 180 C. During this. first stage .of the distillation, care should be exercised to prevent crystallization of naphthalene, if present, such as by employing a condenser operating at elevated temperatures.

When the vapor temperature reached 180 C. at a pressure of 100 mm. Hg absolute, the flame was lowered and the pressure gradually reduced to 20 mm. Hg, absolute, using care to avoid bumping. When a pressure equivalent to 20 mm. Hg, absolute, was reached, the pressure was maintained at that value, and the distillation continued until a vapor temperature of C. was reached.

During the second stage, the condenser may be cooled by cold water, but care should be taken to tavoid the solidification of anthracene, if presen The distillation was conducted rapidly, 5 to 10 cc. of oil per minute being removed.

When a vapor temperature of 195 C. was reached, the source of heat was removed and air 7 was pe tted to enter the apparatus slowly until atmos eric balance was restored.

In the above operation the yield of resin was 29.3%, with an actual melting point of 128 6., which was calculated to be equivalent to a yield of 31.4% at a melting point of 120 C. The color of the resin was light brown.

A straight run A. S. T. M. distillation of 100 cc. of the original oil gave the following data:

As pointed out previously, the high boiling monomeric material derived from tar obtained in the pyrolysis of petroleum, by rapid distillation or solvent extraction methods, may be polymer-- ized to form resins of the type desired by the application of certain catalysts. either with or without the simultaneous, or otherwise, application of heat.

Catalysts such as mineral acids, for example.

sulfuric acid, hydrogen chloride, acids of phosphorus, or acid acting metallic halides or com plexes of said halides, preferably organic solvent complexes, as for example, boron trifluoride, aluminum chloride, boron trifluoride-diethyl ether complex, boron trifluoride-dimethyl ether complex, boron trifluoride-phenyl ether complex, boron triiluoride-phenyi methyl ether complex, boron trifluorlde-dioxan complex, boron trifluoride-toluene complex, correspondingaluminum chloride complexes, and the like, may be employed fonthis purpose.

The metallic halides and their complexes employed are characterized by their ability to hydrolyze in the presence of water to give an acid reaction and, hence, for convenience they may be termed acid acting metallic halides.

Though acid-acting catalysts are preferred, other catalysts may be employed if desired such, for example, as catalysts oi the neutral surface type. Examples of such catalysts are activated clays, silica gel, activated carbon, and the like.

As an example of a convenient procedure for the production of resins of the type desired with the use of sulfuric acid as catalyst, the following is given.

Example 2 A sample of the oil to be polymerized, say 500 cc., is poured into a two-liter 3-neck flask equipped with a thermometer and stirrer. To the oil is added 96% H2804 while agitating vi orously.

The acid is added 1 cc. at a time and the temperature is not permitted to exceed 50 C. The addition of the acid is continued in this manner until no further temperature rise is noted. The amount of acid necessary to achieve this end has been found to be about 1%, by volume, of the oil present, a

The oil then is diluted with approximately an equal volume of naphtha, toluene, or similar diluent, and the solution decanted into 500 cc. of warm water (approximately 60 0.), leaving the acid sludge behind.

After settling, the water layer is drawn off, and

neutralization of the acid is accomplished by use of a 10% to 20% aqueous solution of sodium hydroxide. After washing with caustic, an additional water wash may be made. In either case, the resin solution is dried by filtration through a bed of a suitable drying agent, such as lime.

If desired, the diluent may be added before polymerization instead of after polymerization.

After neutralization and drying, the resin may be isolated from the unpolymerized oil by any desired method, or the resin may be concentrated therein by vacuum distillation, which may be assisted by steam. The melting point of the resin and the yield obtained will depend, among other things, upon the extent to which the resin has been removed from the unpolymerized oil.

A convenient procedure for the production of resins of the type desired by the polymerization of monomeric unsaturated material, derived from tar resulting from the pyrolysis of petroleum, with the use of metallic halide catalysts or metallic halide-organic solvent complex catalysts is illnstrated in the following examples.

Example 3 A 10 gram portion of the selected catalyst is suspended in 300 cc. of benzene by stirring. A 800 cc. portion of the dead oil separated from distillate recovered from petroleum tar emulsion by flash distillation as described'in said oopending application, Serial No. 342.135. is added dropwise from a separatory funnel while maintaining the temperature of the reaction mass below 50 C. When the addition has been completed. the mass is stirred for a period of 2 hours and then neutralized with an aqueous solution of sodium hy-. droxide (10 to 20%). Stirring is continued for an additional hour.

4 Clay or any other desired filter aid then is added and the mass is filtered. The aqueous layer is separated and discarded, after which the treated material is washed with hot water until the washings are-neutral to litmus. The treated material then is filtered through lime to remove water or otherwise dried, and the resin isolated by any desired method.

The unsaturated dead oil employed in the following example was extracted from petroleum tar emulsion, along with light oil, following the procedure described in copending application Serial Number 353,034. After separation or the light oil, the unsaturated dead all was treated in the following manner.

Example 4 A 532.6 gram portion of this unsaturated dead oil was treated with 8 cc. of 66 B. H1804 according to the procedure described in Example 2. Toluene was added after polymerization. Approximately 42% of the dead oil was converted to resin having a melting point of 97 C. and a brown color. The end temperature of the distillation for the removal of oil from the resin was 192 C. and the end pressure was equivalent to 18 mm. of mercury, absolute. A total of 145.9 grams of oil was recovered. The calculated yield of resin having a melting point of C. was 36.2%.

As pointed out previously, the unsaturated dead oil employed for the preparation of resins of the type desired may be polymerized by (a) thermal means, (b) catalytic means, or (c) a combination of thermal and catalytic means. In the latter case. the processes may be carried out consecutively without the intermediate removal of resin,

or the resin may be removed between successive treatments.

The unsaturated dead oil used in the following example was obtained from petroleum tar emulsion by the process 01' copending application Serial No. 342,735. After separation from light oil, it was treated to remove heat polymerizable unsaturates by heating at 200 C. for 4 hours. followed by' removal of the heat polymer resin formed. It was then subjected to catalytic polymerization by the following method.

Example 5 A 500 gram portion of the said unsaturated dead oil was treated with 8 cc. of 66 B. H2804 according to the method described in Example 2. Naphtha was added after polymerization. Approximately 19% of the dead oil was converted to resin having a melting point of 882 C. and a light yellow brown color. The end temperature of the distillation for the removal of oil from the resin was 185 C., and the end pressure was equivalent to 20 mm. of mercury, absolute. A total of 407.9 grams of oil was recovered. The calculated yield of resin having a melting point of 120 C. was approximately 15%.

Examination of the monomeric unsaturated material and associated oil boiling within the range of from 210 to 350 C; described herein and the resins produced therefrom have shown that these materials are predominately aromatic.

Density determinations have indicated that the density of C. of the resins obtained as above described frequently falls within the approximate range of 1.12 to 1.20, with resins produced from dead oil from the solvent extraction of tar tending to be somewhat higher than those produced from dead oil from rapid tar distillation. The densities of the acid polymers tend to be somewhat lower than those of the heat polymers derived from the same unsaturated dead oil. Resins of this type having other densities may be employed, however.

The molecular weights of the resins produced as previously described necessarily vary with the melting point, which also varies with the presence of varying quantities of associated oil among other factors. Determinations by the Benzene Freezing Point Depression method have shown such resins usually have molecular weights rang! from 80.5 to 195 C. as determined by the cube in mercury method.

The fracture of the high melting point resins described herein may range from conchoidal to hackly. In general, the polymers are quite brittle.

The resins described herein, except those hardened by exhaustive steam distillation to a very high melting point, will usually react positively to the anthraquinone reaction, indicating the presence of anthracene, unless produced from lower boiling portions of the dead oil, which do not contain anthracene, or unless the anthracene has been otherwise removed.

The resin described herein usually will give but a slight diazo reaction, indicating the substantial absence of phenols.

The resins produced as described usually will give negative Lieberman Storch reactions, indicating the absence of rosin acids.

Upon thermal decomposition of the resins of the type produced as above described herein, ap-- preci'able yields of material boiling within the range from 210 C. to 350 C. will be produced.

The heat polymer resins of the type produced 10 as above described usually are substantially completely soluble in carbon disulflde and benzol.

The quantity of resin insoluble in a mixture containing 50% petroleum ether and 50% D tane varies with the melting point of the resin,

and may be of the order of 52% in the case of a thermal resin having a melting point of 95 C.

and of the order of in the case of a thermal resin having a melting point of approximately 183 C. (Cube in mercury method.)

The quantity of resin of the type produced as above described insoluble in a mixture of 50% petroleum ether and 50% pentane, but soluble in CCl4, may be of the order of 50% for a thermal resin having a melting point of C. and of the order of 74% in the case of a thermal resin hav- (Cube in mercury I 'cohols.

The polymers from unsaturated dead oils obtained from the rapid distillation process described in copending. application, Serial No. 342,- 735, tend to be more soluble in those solvents tried than similarly produced polymers from unsaturated dead oils obtained by the solvent extraction process described in copending application,

Serial No. 353,034.

The above described characteristics of color, density, fracture, melting point, molecular weight, dlazo reaction, Lieberman Storch reaction, anthraquinone reaction, thermal decomposition, and solubility are given for the purpose of illustration. It is not intended to imply-necessarily thatthe resin produced as described above and employed herein may not depart somewhat from this illustrative description in one particular or more.

Furthermore, the addition of other materials to the heat polymerizable monomeric unsaturated materials prior to polymerization or to the resins after polymerization may of course modify the properties of the resins produced. Examples of such materials are other synthetic or natural resins, plasticizers, softeners, fillers, coloringmaterials, etc. 7

The resin employed may comprise mixed polymers of monomeric material boiling within the range of from 210 C. to 350. 0., together, if desired, with polymers of monomers boiling outside of this range, or resins may be employed which are produced from monomers boiling within a selected range or ranges within the range of from 210 C. to 350 C. for instance from separated material boiling above, say, 250 C. or, say, above In separating such material, the dead oil containing the monomers may be fractionated by avoid undue polymerization during the separation, or other methods of separation may be employed.

As previously pointed out, the herein described resins, namely, those obtained by thethermal and/or catalytic polymerizationof the unsaturated monomeric material recovered from the tar formed during the production of gas by processes involving the pyrolytic decomposition or conversion Oi ydrocarbon oil, with or without the aid Examples of suitable treating agents are oxy- 7 gen. air, ozone, and various organic and/or inorganic peroxides, such as benzoyl peroxide, hydrogen peroxide, sodium peroxide, and the like. The use of air is preferred.

The solid resin maybe treated with oxygen,

among other ways, by (a) exposing the resin in the form of a thin sheet or film-such as .a film deposited upon a suitable metallic drum or other surface. or (b) by exposing the resin in finely divided or powdered form, to the action of oxygen, such as by permitting the powdered resin to fall through a vertical tower or vessel, or by agitating the iinely divided powder, in the presence of oxygen or air. Such treatment preferably is carried out at elevated temperatures, such as temperatures in the range of 35 to 150 C., or even higher.

Another method of contacting the resin with oxygen comprises melting the resin and passing air or oxygen through the molten resin. A variatlon of this method comprises the addition of an organic and/or inorganic peroxide to the molten resin.

A preferred method of contacting the resin and oxygen comprises dissolving the resin in a suitable solvent, preferably substantially inert to the resin, such as a hydrocarbon solvent, for example an aromatic hydrocarbon solvent having no unsaturation other than in benzene rings. preferably boiling below 200 C., such as, xylene, and passing air or oxygen through the resin solution, preferably at elevated temperatures. A variation of this method comprises the addition of an oxygen yielding agent, such as an organic and/or a'n inorganic peroxide, to the resin solution.

Finally, the monomeric unsaturated high-boiling aromatic material from which the resin is derived may be treated prior to, or, during 'polymerization with oxygen, such as by passing a stream of air or oxygen through the material. If desired, this may be carried out at elevated temperatures. in which case a combination of inhibitor removal and polymerization is achieved. A variation of this method involves the addition of an oxygen yielding material, such as an organic and/or inorganic peroxide, to the monomeric marial prior to, or during, polymerization.

. Another method comprises contacting the polymerized high-boiling aromatic material with oxygen and/or an oxygen yielding substance prior to the removal of the unpolymerized material.

Any of the foregoing treating processes may be carried out at any desired temperature, although 1 generally prefer to employ temperatures in the range of 30 to 200 C. and more particularly 50 to 150 0., for this purpose.

When solvents are employed, they are preferably stable in character. I prefer to employ hydrocarbon. and more particularly aromatic hydrocarbon, solvents.

Catalysts also may be employed to assist in the oxidation process. I have found that metallic oxides and compounds, particularly manganese compounds such as potassium permanganate, are

eifective'catalysts for this purpose.

I have found further that metallic compounds and particularly manganese compounds 10 as i2 metallic permanganates. for example, potassium permanganate, are particularly eflective catalysts when used in conjunction with ketones such as acetone.

The process may be illustrated by means of the following examples.

Example 6 A resin of the type prepared in Example 1 1 is melted, after which a stream of air is passed through the molten resin for a period of two hours with agitation. A resin possessing excellent drying properties is obtained.

Example 7 Example 8 This is a repetition of Example 7, with the exception that the resin solution obtained in Example 1 is used prior to the removal of unpolymerized material. After oxidation and removal of the unpolymerized material, a resin possessing good drying properties is obtained.

Eiample 9 A sample of the monomeric unsaturated high boiling aromatic material described herein is treated with a stream of air for a period of one hour at 50 C. The treated material is polymerized according to the method described in Example 1, whereupon a resin possessing excellent drying properties is obtained.

Coating compositions of the type described;

herein usually are prepared by incorporating the treated resin in a drying oil or bodied drying oil, followed by thinning the resulting mixture by the addition of a suitable solvent, such as a hydrocarbon solvent. Driers may be added to the mixture, as well as pigments, coloring agents, plasticizing' agents, antiskinning agents, fillers, and/or other additives.

Examples of drying oils which may be employed in preparing my new coating compositions are tung oil, oiticica oil, perilla oil, dehydrated castor oil, fish oil, sardine oil, menhaden oil, linseed oil, soya been 011, synthetic and/or modified drying oils, and the like.

Examples of thinners are hydrocarbon solvents derived from petroleum oils or cracked products, such as mineral spirits. V. Msand P. naphtha, and the like, hydrogenated and/or modified hydrocarbon solvents, coal tar solvents, such as toluol, xylol, and solvent naphtha, and similar materials.

Driers which may be used include the lead, manganese, and/or cobalt salts of high molecular weight organic acids, such as metallic resinates. naphthenates, oleates, and the like.

Pigments which may be incorporated in coating compositions of the type described include white lead, lead'chromate, titanium oxide, red lead, zinc oxide, lithophone, chrome yellow, iron oxide, ochre, ultramarine blue, Prussian blue. lampblack, carbon black, and the like.

A preferred method of incorporating the treated resin in the drying 011 comprises heating a mixture of the drying oil and treated resin to a suitable temperature for a period of time sumcient to insure the desired body. The mixture then is reduced to the desired viscosity by the addition of a suitable solvent, such as mineral spirits.

An alternative method comprises heating the 14 blending or mixing in a suitable mill or other device, such as a ball mill or a roller mill. 'I'he incorporation of pigments in such coating comdrying oil, or a mixture of the drying oil and a\ portion of the treated resin, to the desired bod ing temperature, and adding the treated resin,

or the remainder of the treated resin at some stage of the bodying process. After the desired body had been attained, the mixture may be reduced by the addition of a suitable solvent.

The treated resin. or any portion of it, also may be used to check the bodying oi the drying oil at any desired stage.

25 gallons, and particularly under 20 gallons, are

employed. Excellent results are secured in practically all cases when coating compositions having oil lengths of 15 gallons. or less, are employed.

Thus, for example, coating compositions possesslng unusually desirable properties are obtained from linseed oil and a treated resin or the.

type described herein when such compositions have an oil length of from 6 to 10 gallons.

In a similar manner, excellent results are obtained with both perilla oil and fish oils when the resulting coating compositions have an oil length of gallons, or less.

At higher oil lengths, the coating compositions may be slightly unstable. fested by the precipitation of a portion of the resin from the coating composition during storage.

The foregoing preferred oil lengths pertain particularly to coating compositions in which petroleum hydrocarbon fractions such as mineral spirits or V. M. and P. naphtha, have been employed as solvents. In case a coal tar solvent, ormixture of coal tar solvent and petroleum hydrocarbon fraction. is used as the solvent, the indicated oil lengths can be increased substantially without seriously impairing the properties of the resulting coating compositions.

The oil lengths discussed in the foregoing paragraphs refer to the number of gallons of drying oil employed for. each hundred pounds of treated resin.

, The incorporation of a treated resin of the type described herein in a typical 15 gallon varnish is illustrated by the following example.

Example 10 A mixture of the treated resin and linseed oil is heated to a temperature of 580 F., after which it-is held at this temperature for a period of one hour. The varnish then is reduced to 50% solids by the addition of mineral spirits.

A quantity of cobalt and lead naphthenates equivalent to 0.6% lead and 0.2% cobalt, expressed in terms of the respective metals as a percentage of the drying oil present, is added to the varnish when it reaches room temperature. A varnish having excellent drying properties is obtained.

Coating compositions of this type may be used as such for application to a wide variety of surfaces, or they may be modified by the addition 01 other ingredients before application.

Thus, for example, pigments may be incorporated in the varnish obtained in Example 10 by- This is usually manipositions is greatly facilitated by the exceptional wetting and dispersing properties of the treated resins oi the type .described herein, resulting in a marked decrease in the time required to produce a given enamel.

I at least 98% and more particularly, to at least Lesser quantities of other resins may be incorporated in the coating compositions of the typ described. if desired. In general, however, I prefer to employ treated resins or the type described herein'as the sole resinous ingredient oi. the coating composition.

The excellent durability of coating compositions prepared from treated resins of the type described herein is illustrated by the following examples:

Example 11 A 15 gallon perilla oil varnish prepared from the resin obtained in Example 1 had a drying time of 20 hours. A similar, varnish prepared from the treated resin obtainedas in Example 6 had a drying time of only 7-8 hours.

To summarize, the --:hydrocarbon polymers or resins treated in accordance with this invention may be characterized as follows:

(1) The polymers or resins are comprised of carbon and hydrogen in chemicalcombination to 99%. other elements such as oxygen, nitrogen and/or sulfur derived from the oil pyrolyzed, if present, being restricted to less than 2%.and more particularly to less than 1%.

(2) The polymers or resins are substantially completely soluble in an excess of benzene, the proportion of insoluble material being less than 1%, and more particularly, less than 0.1% of th polymer or resin.

(3) The polymers or resins have an ash content determined by burning of less than 1%, and more particularly, of less than 0.1%.

(4) Upon subjecting the polymers or resins to destructive distillation under vacuum to efl'ect deing points of at least 40 C. and more particularly of at least C. For example, typical polymers or resins polymerized by surface active agents such as clay, as catalysts, have A. S. T. M. ball and ring softening points of at least 40 0., such as between 60 C. and 80 C. or above. and typical polymers or resins polymerized by heat, or with acid or acid-acting catalysts, have A. S. T. M. ball and ring softening points of at least 80 C., such as between and C. and higher, such as up to C. or above.

(b) They have densities of at least 1.10 and up to 1.20 and higher, such as between 1.13 and 1.18, as determined by the water displacement method.

(0) They have molecular weight between 300 and 1000as determined by the freezing point depression method employing benzene as the solvent.

(d) They have a solubility in an equal quantity by weight of toluene at a temperature of C. of at least grams, and preferably of at least trams, in 100 grams of toluene.

(e)-- One part or the polymers or resins when dissolved in three parts by weight of benzene having a density (dzo) of 0.8790 and a refractivity intercept of 1.0623, makes four parts of a solution having a density greatzr than 0.925 and a re- !ractivity intercept greater than 1.069. Neglecting any possible change that may occur in the solid when it is dissolved, calculated values for the polymers or resins themselves, that is, apart from the solvent, (densities and rerractivity intercepts being additive on a volume basis) become for densities at least 1.10, and for refractivity intercepts at least 1.08, and particularly, at least 1.09, and still more particularly,at least 1.10.

(6) The oils from which the polymers or resins are polymerized have mixed aniline points below 15 C., and more particularly, below 10 C., for example, between 10 and 4 C. and lower. A mixed aniline point of a given oil is defined as the critical solution temperature of a mixture of 10 cc. of

- anhydrous aniline, 5 cc. of the'oii being tested and 5 cc. of a petroleum naphtha having an anitentative standard D611-41T.

(7) The oils from which the polymersor resins line point of C. as determined by A. S. T. M.

are polymerized usually having refractivity intercepts 01' not less than 1.08, for example, between 1.09 and 1.11, and higher, such as, up to 1.125 or (8) The oils from which the polymers or resins are polymerized contain at least such as not less than and more particularly not less than 97% of aromatic hydrocarbons.

(9) The oils from which the polymers or resins are polymerized have densities of not less than 0.95, and, more particularly, of not less than 0.98, for example, between 0.99 and 1.02, and higher, such as up to 1.11 or 1.12.

(10) Liquid material extracted from the polymers or resins using a large excess of pentane has refractivity intercepts or at least 1.08 and more particularly, of at least 1.09, and still more particularly, of at least 1.10.

(11) The oil separated from the polymers or resins after polymerization usually has a density or not less than- 0.95 and, more particularly, of not less than 0.98, for example, between 0.99 and 1.02 and higher, such as up to 1.11 or 1.12. Such oils separated from the polymers or resins after polymerization also usually have relractivity intercepts of not less than 1.08, for example, between 1.09 and 1.11, and higher, such as up to 1.125 or 1.135, and contain at least 90%, such as at least 95%, and more particularly, at least 97% arematic hydrocarbons.

(12) Reriractivity intercept when referred to herein is determined by the method described in the Science of Petroleum (1938), vol. 2, beginning on page 1175, and publications referred to therein.

In the specification and in the claims the term "treated resin" is intended to mean a resin or the type described herein, the said resin and/or the monomeric material from which it is prepared having been treated with oxygen and/or an oxygen-containing and/or oxygen-yielding material.

While various procedures and formulas have been particularly described these are of course subject to considerable variation. Therefore, it will be understood that the foregoing specific ex- 16 scope or the claims without departing from the spirit of the invention, which is intended to be limited only as required by the prior art.

I claim:

1. A coating composition comprising a drying oil and a hydrocarbon resin polymer selected'i'rom the group consisting of heat resin polymer and catalytic resin polymer of polymerizable hydrocarbons contained in a hydrocarbon oil which has been physically separated from tar produced in the vapor phase pyrolysis of petroleum oil and which is free from and of greater volatility than the pitch oi? said tar, said hydrocarbon oil when separated and when subjected to polymerization containing in addition to hydrocarbons boiling between 210 C. and 350 C. which are not polymerizable by the application to said oil of heat alone but which are polymerizable to catalytic resin polymer by treating said oil with a resinproducing catalyst, other hydrocarbons boiling between 210 C. and 350 C. which are polymerizable to catalytic resin polymer by treating said 011 with a resin-producing catalyst but which lastmentioned hydrocarbons are also polymerizable to heat resin polymer by the application to said oil of heat alone, said last-mentioned hydrocarbons being present in said hydrocarbon oil in amount greater than approximately 5% of the total hydrocarbon oil boiling between 210 C. and 350 C., the proportion of drying oil to resin polymer being such as to produce a coating composition having an oil length of less than 25 gallons, in the said resin the drying inhibitors naturally present in the resin as produced having been removed by reaction with oxygen at a temperature within the range of 30 C. to 200 C. in a solution of the said resin to improve the properties of the resin for inclusion in coating compositions.

amples are given by way of illustration, and that changes, omissions, additions, substitutions and/ or modifications might be made within the 2. As a new composition of matter, a hydrocarbon resin polymer selected from the group consisting of heat resin polymer and catalytic resin polymer of polymerizable hydrocarbons contained in a hydrocarbon oil which has been physically separated from tar produced in the vapor phase pyrolysis of petroleum oil and which is iree from and of greater volatility than the pitch of said tar, said hydrocarbon oil when separated and when subjected to polymerization containing in addition to hydrocarbons boiling between 210 C. and 350 C. which are not polymerizable by the application to said 011 or heat alone but which are polymerizable to catalytic resin polymer by treating said oil with a resin-producing catalyst, other hydrocarbons boiling between 210 c. and 350 C. which are polymerizable to catalytic resin polymer'by treating said oil with a resin-producing catalyst but which last-mentioned hydrocarbons are also polymerizable to heat resin polymer by the application to said oil of heat alone, said last-mentioned hydrocarbons being present in said hydrocarbon oil in amount greater than approximately 5% 01 the total hydrocarbon oil boiling between 210 C. and 350 C., in the said resin the drying inhibitors naturally present in the resin as produced having been removed by reaction with oxygen at a temperature within the range of 30 C. to 200 C. in a. solution of the said resin to improve the properties of the resin for inclusion in coating compositions.

3. A process for improving the properties for inclusion in coating compositions of a hydrocarbon resin polymer selectedi'rom the group consisting'of heat resin polymer and catalytic resin polymer of polymerizable hydrocarbons contained in a hydrocarbon oil which has been physically application to said oil of heat alone but which are polymerizable. to catalytic resin polymer by treating said oil with a resin-producing catalyst, other hydrocarbons boiling between 210 C. and

350 C. which are polymerizable to catalytic resin polymer by treating said oil with a resin-producing catalyst but which. last-mentioned hydrocarbons are also polymerizable to heat resin polymer by the application to said oil of heat alone, said last-mentioned hydrocarbons being present in said hydrocarbon oil in amount greater than approximately 5% of the total hydrocarbon oil boiling between 210 C. and 350 0., which comprises forming a solution of the said resin in a solvent therefor, and removing from the resin drying inhibitors naturally present therein as the said resin is produced by reacting the resin in solution with oxygen at a temperature within the range of 30 C. to 200 C.

4. A coating composition comprising a drying oil and a hydrocarbon resin polymer selected from the group consisting 01' heat resin polymer and catalytic resin polymer or polymerizable hydrocarbons contained in a hydrocarbon oil which has been physically separated from tar produced in the vapor phase pyrolysis of petroleum oil and which is free from and of greater volatility than the pitch of said tar, said hydrocarbon oil when separated and when subjected to polymerization containing in addition to hydrocarbons boiling between 210 C. and 350 C. which are not polymerizable to catalytic resin polymer by treating said oil with a resin-producing catalyst, other hydrocarbons boiling between 210 C, and 350 C. which are polymerizable to catalytic resin poly- .mer by treating said oil with a resin-producing catalyst but which last-mentioned hydrocarbons are also polymerizable to heat resin polymer by the application to said oil of heat alone, said last- 18 arated and when subjected to polymerization containing in addition to hydrocarbons boiling between 210 C. and 350 C. which are not polymerizable by the application to said oil of heat alone but which are polymerizable to catalytic resin polymer by treating said oil with a resinproducing catalyst, other hydrocarbons boiling between 210 C. and 350 C. which are polymerizable to catalytic resin polymer by treating said oil with a resin-producing catalyst but which lastmentioned hydrocarbons are also polymerizable to heat resin polymer by the application to said oil of heat alone, said last-mentioned hydrocarbons being present in said hydrocarbon oil in amount greater than approximately 5% of the total hydrocarbon oil boiling between 210 C. and 350 C., in the said resin the drying inhibitors naturally present in the resin as produced having been removed by reaction with oxygen at a temperature within the range of 30 C. to 200 C. and in the presence of a metallic oxide oxidation catalyst in a solution of the said resin to improve the properties of the resin compositions.

6. A process for improving the properties for inclusion in coating compositions of a hydrocarbonresin polymer selected from the group consisting of-heat resin polymer and catalytic resin polymer of polymerizable hydrocarbons contained in a hydrocarbon oil which has been physically separated from tar produced in the vapor phase pyrolysis of petroleum oil and which is free from and or greater volatility than the pitch of said tar, said hydrocarbon oil when separated and when subjected to polymerization containing in addition to hydrocarbons boiling between 210 C and 350 C. which are not polymerizable by the application to said oil of heat alone but which are polymerizable to catalytic resin polymer by treating said oil with a resin-producing catalyst, other hydrocarbons boiling between 210 C. and 350 C.

' which are polymerizable to catalytic resin polymentioned hydrocarbons being present in said hydrocarbon oil in amount greater than approximately 5% of the total hydrocarbon oil boiling between 210 C. and 350 C., the proportion of drying oil to resin polymer being such as to produce a coating composition having "an oil length of less than 25 gallons, in the said resin the drying inhibitors naturally present as the resin is produced having been removed by reaction with r ygen at a temperature within the range of 30 C. to 200 C. in a solution of the said resin and in the presence of a metallic oxide oxidation catalyst to improve the properties or the resin for inclusion in coating compositions. p

5. As a new composition or matter, a hydrocarbon resin polymer selected i'rom the group consisting oi heat resin polymer and catalytic resin polymer of polymerizable hydrocarbons contained in a hydrocarbon oil which has been physically separated from tar produced in the vapor phase pyrolysis of petroleum oil and which is free from and oi. greater volatility than the pitch 01' said tar, said hydrocarbon oil when sep mer by treating said all with a resin-producing catalyst but which last-mentioned hydrocarbons are also polymerizable to heat resin polymer by the applicationto said oil of heat alone, said lastmentioned hydrocarbons being present in said hydrocarbon oil in amount greater than approximately 5% of the total hydrocarbon oil boiling between 210 C. and 350 C., which comprises forming a solution of the said resin, and removing from the resin drying inhibitors naturally present therein as the said resin is produced by reacting the resin in solution with oxygen at a temperature within the range of 30 C. to 200 C. ,and in the presence 01' a metallic oxide oxidation catalyst.

FRANK J. SODAY.

REFERENCES crrnn The following references are of record in the file ofthis patent:

UNITED s'ra'ms PATEN'ILS I Date for inclusion in coating 

